Condensation products and process for preparing same



Batented Aug. 4, 1936 U TE TA ES AT NT-.OF E

mummies rnonucrs AND raocess y FOR'PREPARING SAME erbert Hiinel, Klosterneuburg-Weidling, near Vienna, Austria,

assignor to Beck, Keller 8;

Company, Inc., Detroit, Mich., acorporation of Delaware No Drawing. Application May 4, 1932, Serial No. 609,337. In Austria August 6,1927

. 15 Claims. This invention relates tc an improvement in condensation products of the phenol formalde 362,460, filed May 11, 1929, entitled Artificial mass and process for making same, now Patent No.'

1,800,296, granted April 14', 1931.

According to my Patent No. 1,800,295, I have ascertained, that by condensing together aldehydes and phenols substituted in the para position bya higher saturated hydrocarbon radicle,

resinous products can be obtained, which are I completely and readily soluble in petroleum hydrocarbons and possess highly valuable proper ties.

The substituents may bealiphatic or hydroaromatic radicles, as e. g. the p-tertiary-butylor the p-tertiary-amylor the p cyclohexyl-group, which can be easily introduced by means of different methods;

.Now I have found away which is particularly suitable for the production of heat hardening solid resinous condensation products from paratertiary-butylphenol and a considerable excess of formaldehyde over the equimolecular proportion.

These'resins yield, by reacting them under heat with drying oils (preferably China wood oil), very excellent bases for varnish manufacture which 1 are superior to those prepared from liquid or crystalline condensation products and drying oils.

First I prepare a condensation product in the same way as described in my Patent No. 1,800,295

above referred to. This process comprises leav-' ing in contact the phenol body and aqueous commercial formaldehyde solution and such a quan 'tity of astrong alkali so that 'a clear solution-of the constituents occurs. The temperature. may

be the ordinary one or moderately elevated. vAfter the formaldehyde has been boundwhich takes "(omen- 4) q I precipitate the 'condensation'product from its alkaline solution byneutralizing the latter with any substance of acidic character. Elevated temperature may be used in this process'in orderv to obtain a well settled condensation product. In

order to obtain a pale resin which will also yieldpale and "clearproducts when reacted under elevated temperature conditions with drying oils andthe like, an efiort should be made to secure an."

exact neutralization ofthe alkaline catalyst. The aqueous phase isseparated from the" condensation product and the latter may optionally be washed by repeatedly mixing same thoroughly with water and separating the two layers. The

condensation product, depending upon the tem:-.

perature employed and upon the length of time respectively,- will be of a thin liquid nature or more or less viscous or even solid at ordinary room temperature. In the latter cases, elevated temperatures must be used any way for precipitatwashing the same.

Now I'heat the condensation product slowly up to temperatures or about 120150 C. until I obtain a clear solid resin of any desired degree of hard ness or any desired melting point. The mechanically adhering as 'well'as the chemically formed water escapes the reaction mass 'due to the heat treatment and the continued condensation reaction. In case" the condensation product is already a solid mass at ordinary roomtemperature as expl'ained above, the employment of a vacuum'is a'd-'- visable, asotherwise" an undesirable high stage of condensation may occur before the'water has v evaporated. Naturally-'the moist solid condensation product can also be pulverized and dried in the simplest way. Hereupon item be used. as

such, or can be melted into a clear resin which; may be kept at an elevated temperature if a still higher stage of condensation is desired.

According to my opinionthe originally formed mixture of the 'butyl phenol-monoand dialcoholiwhich represents a low viscous oil,forms,-b'oth after being precipitated and-when still being in V ing and neutralizing the condensation product or alkaline aqueous solutiomphenol alcohols of higher molecular polynuclear phenols which have more or less resinous properties.

, I1 moleculadialcohol {l- 2 melemiles monoalcohol etc.

between 1 to 1 0 days according to the temperature and the proportion of formaldehyde employed,

On account of their CHaOH groups such compounds can undergo. further condensations, most- 2 lyimdersplittingofiofwaterfornfinghigher melting. resin and finally eventually insoluble 1 and infusible brown m.

The method of producing the comparatively the condensation of the phenolbodv with formali dehyde in the presence of a strong acidic catalyst until a viscous condensation product has been formed and then by continuing the condensation in an alkaline medium, in a manner similar to that described in the aboveparagraph.

In the acidic medium the formation of various higher molecular polynuclear phenols may ooour, whilst in the succeeding alkaline medium the v entrance of 0112011 groups may occur. The final condensation product will be of a similar structure as the formula shown above indicates; and it reallybehavesinthesamewayastheresins which are obtained by employing the alkaline medium from the beginning.

However, the simplest and preferred method, as

described above, is to work only in an alkaline m medium and in such a manner that a condensation product is obtained which is still in the liquid stage at ordinary room temperature, and to thereafter transform the liquid condensation product into a solid resin by heating the same.

Finally it should be mentioned, that instead of using chemically pure butyl-phenol, technically crude products can be used which are obtained according to the known methods.. Such prod-, ucts usually contain small amounts of orthobutyl-phenol and di-(ortho-para-) 1butyl-phenol as byproducts where the para butyl-phenolds the main constituent.

The solid reactive condensation product of the soluble stage obtained by any of the described methods can be worked up togetherwith a suitable amount of drying oils and other materials commonly employed in varnish manufacture in the same way as the lower molecular oily or, viscous products themselves from which theyare derived. The reaction of the latter with drying oils etc. has been described in my copendingearlier applications to' which I referred above. But the solid products yield by reacting them with the oils etc. still more highly valuable for varnishes than the liquid ones do. I believe that the CHsOH groups of the resin which causes the continued condensation undergo also certain reactions with the 'drying' oils when heated together in a similar manner as I have already explained in my Patent No. 1,800, 96.

combination products, even of comparatively small amounts of the reactive resins with oils show a much higher viscosity than the oils themselves. Such resins, which by prolonged heat-,

ing finally become infusible, need a certain minimum of the oil, as otherwise the entirerreacting mixture will yield a gelatinous mass which can only swell in solvents. This amount of oil dependsupontheviscosity oitheoilitselflthe mixing of the two viscosity, the higher its minimum In accordance with my earlier applications, the dryingoilsmay bereplacedwholly orpartlyby altered (e. g. heat treated) drying oils or by 5 non-drying oils or otherbases of the varnish manufacture. Such bases may be either ordinary or altered natural resins or artificial resins or compounds or mixturesof such resins with drying oils as e. g. mixed glycerol esters, the saponification of which yields polybasic acids and unaltered or altered fatty acids and occasionally natural resinous acids on the one hand and glycerol on the other. Suchesters are not of a typically resinous. nature, but are of relatively low viscosity,and are more or less oily. Suitable mixed glycerol esters of this kind have been described in my Patent No. 1,800,296.

By reacting all those mentioned products with the above describedreactive resinous products 26 from .p-tertiary-butylphenol and formaldehyde in suitable Pr portions I have always obtained a very remarkable increase of their durability. toughness, resistance etc. v

A small amount of such materials or their mix- 26 tures may optionally be present already during the above described formation of the solid products from the oily or viscous ones and may be a constituent of the final reactive solid'product. Provided, a proper relative amount of formalde- 30 hyde has been employed, mixing product nevertheless will become infusible when heated alone. a

'Ihe following examples are only intended to illustrate the methods and it will be understood 35 that theprinciples of my invention are neither limited to specific proportions given in the examples nor to the temperatures etc. employed.

- Emmplc 1 100 parts of p-tertiary-butylphenol and parts of commercial 40 per cent. formaldehyde solution are left in contact in the presence of, 15 parts of 40 per cent. caustic soda solution. Care must be taken, thatv the temperature does not rise above about 80 C. in order to avoid a considerable loss of formaldehyde. The phenol body soon dissolves and melts due to the reaction heat and forms, a clear, solution with the other ingredients. The alkaline solution is maintained at about 40 C. for one week and by neutralizing same with acidic substance, the oily reaction product is precipitated. After separating the latter from the supernatant aqueous liquid, it is heated for about 2 hours at C. and then higher up to about C.a'nd is kept at this temperature for about half-an-hour.

115 parts of a clear pale resin are obtained hereby, which is readily soluble in benzine and other hydrocarbons and many other solvents. It 60 is also very easily soluble in drying oils. When hither its ammt.

heated alone for a prolonged time at about C. it is converted into an infusible and insoluble dark'brown condensation product.

when heated together with about 300 parts of as China wood oil up to finally 230' C., I obtain about 405 parts of a pale. hishLv viscous combination product which represents a very valuable by about 600 parts of a moderately bodied oil and 200v parts or ester gum (rosin-glycerol ester) or of pale coum'arone resin.v In the latter cases I first melt the gum with the oil under stirring and then' add the resinous condensation *prod- I uct.-

.1 Example 2 100 parts of the p-tertiary-butylphenol are heated in a container provided with a return condenser with 30 :parts of commercial aqueous30 percent. formaldehyde solution and with 4 parts of concentrated hydrochloric acid, until the odor of the formaldehyde has disappeared. The water is separated from the highly viscous conden- 120 C. is sufllcient to produce a solid condensation product with the properties of the prod-' not of Example 1. When heated with oils and the like it behaves similarly.

For instance, I combine the product (1 part) with the. viscous mixed glycerol ester prepared from 1 part of camphoric acid, parts ofzAmerican wood rosin, /g part of linseed oil fatty acids, part of glycerol and 2 parts of China wood oil and /2 part of linseed oil, by heating the whole reactive mixture upto about 240 C. The final product represents a very-tough slightly sticky mass, which is readily soluble in common solvents and can be used similarly to a common oil varnish, but which possesses extremely good qualities. The camphoric acid may be replaced by other polybasic acids or their anhydrides, as e. g. about parts of phthalic' anhydride or phthalic acid or about parts. of adipic acid or about /3 part of maleic acid and so on.

Example 3 100 partsof a technical p-tertiary-butylphenol which contains 1 to 2 per cent. ortho-butylphenol and 5 to 10 percent. di-tertiary-butylphenol (ortho-para) and occasionally-1 per cent. of meta-butylphenol as byproducts and BO'parts of commercial 40 per cent. formaldehyde solution and 10 parts of 40 per cent. caustic soda are heated to 60 C. for 3 days. Such an amount of alcohol is added as to form a clear mixture and additional amounts of alcohol are added whenever a separation into two layers occurs during the condensation. The condensation product is precipitated and carefully neutralized in the heat at about to C. by adding diluted hydrochloric acid and repeatedly washed with water. The main amount of alcohol is by this means removed. The moist condensation product solid at ordinary room temperature, is pulverized and left to dry. It represents a resin with a melting point of about 50 C. and can be worked up as such with'drying oils and the like as explained in the foregoing examples or it is melted and heated to about C. until a resin with a melting point of 80 to 90 C. is obtained, whereupon it can be employed for preparing varnishes and the like.

Both the lower melting resin and the higher melting resin can be worked up in the heat with an ,:esterlike product which has been prepared as follows: I a

are heatedat 200 C. under stirring until a. um-

g f Grams Abietic acid -100 Castor oil fatty acid.: '50 Methyl-isopropyl-endoethylene-tetrahydrophthalic'acid 50 Maleic acid v 1 Glycerine J 50 form melt has been formed. Then 200 grams of castor oil are added gradually and the temperature is raised to 270- and kept until the acid number has dropped to 25 window. The resulting product constitutes ahighly viscous mass.

100 grams of one of the resins obtained above are dissolved in the mass at about C. whereupon the temperature is raised to 230 C. or higher. A soft highly elastic resin is obtained which may be used as a plasticizer in nitrocellulose lacquers.

In the foregoing-examples I have restricted myself to the meet ordinary pressure, but it is obvious that the employment of different pressures, particularly reduced pressures, also falls withi the scope of my invention. y

It will be understood that thedisclosures of my prior Patents Nos. 1,800,295 and 1,800,296 are to be considered as part of the disclosure of the present specification.

My inventionis broadly applicable'to a very 0 large number of ester-like substances, as has been disclosed in my prior Patent No. 1,800,296. The solid condensation products hereinbefore referred to may therefore be reacted equally-wellwithany volatile.

What I claim is: V I 1. Aprocess of preparing an oil soluble resin which is solid at ordinarytemperature and capable of undergoing further condensation on the practically neutral ester-like body which is nonapplication of heat, from para-tertiary-butylphenol, which process comprises maintaining the phenol and a substantial excess or formaldehyde over the equimolecular quantity in contact for a prolonged period o't'timeat moderate temperatures in the presence of a strong alkaline catalyst,

whereupon the condensation product formed hereby is further condensed by the application of heat into a solid resin, the process including neutralizing the catalyst. l

2. A process'of preparing an'oil soluble resin which is solid at ordinary'temperature and capable of undergoing further condensation on the application of heat. from para-tertiary-butylphenol, which process comprises maintaining the phenol and a substantial excess of formaldehyde over the equimolecular quantity in contact for a prolonged period of time at moderate temperatures in the presence of a strong alkaline catalyst, whereby a quantity of formaldehyde corresponding with 1-2 mol. per each mol. or the phenol is compounded, whereupon the condensation product formed hereby is further condensed by the application of heat into a solid resin, the process including neutralizing the catalyst.

3. A process of preparing an oil soluble resin which is solid at ordinary temperature and capable of undergoing further condensation on the application of heat, from para-tertiarybutyl-' phenol, which process comprises (1) maintaining the phenol and a substantial excess of formaldehyde over the equimolecular quantity in contact for a prolonged period of time at moderate temperatures in the presence of a strong alkaline catalyst, whereby a quantity of formaldehyde corresponding with 1-2 moi. per eachmoi. of the I phenol is compounded, (2) neutralising the alkaline catalyst by acidifying the reaction mixture and (3) converting the thus obtainedliquid condensation product into a solid resin by the application of heat.

4. A process of preparing an oil soluble resin which is solid at ordinary temperature and capable of undergoing further condensation on the application of heat, from para-tertiary-butylphenol, which process comprises (1) maintaining the phenol and a substantial excess of formaldehyde over the equimolecular quantity in contact for a prolonged period of time at moderate temperatures in the presence of 'a strong alkaline catalyst, whereby a quantity of formaldehyde corresponding with 1-2 mol. per each mol. of the phenol is compounded, and (2) heating the reaction mixture at considerably elevated up to boiling temperatures for such a period of time that on neutralizing the reaction mixture a condensation product is precipitated which is solid at ordinary temperature.

5. A process according to claim 1, in which diminished pressure is employed in order to dry the condensation product.

6.Aprocessaccordingtoc1aim1,inwhicha homogenizing agent mixture.

7. A modification of the process according to claim 1, whichcomprises'starting'the condensation of the phenol body with formaldehyde in the presence of an acidic catalyst until a viscous condensation product has been formed and continuing the condensation in an alkaline medium.

8. An oil soluble resin which is solid at ordinary temperature and capable of undergoing further condensation on the application of heat, obtained by maintaining para-tertiary-butylphenol and a substantial excess of formaldehyde over the equimolecular quantity in contact for a prolonged period of time at moderate temperatures in the presence of a strong alkaline catalyst, whereupon the condensation product formed hereby is further condensed by the application of heat into a solid resin, the process including neutralization of the catalyst.

9. An oil soluble resin which is solid at ordinary t mp atur and capable of undergoing further condensation on the application of heat. obtained by maintaining para-tertiary-butylphenol and a substantial excess of formaldehyde over the equiis added to the reaction molecular quantity in contact for a prolonged periodoftimeatmoderatetemperaturesinthe presence ofa strong alkaline catalyst, whereupon the condensation product formed hereby is further condensed by the application of heat into a 5 solid resin, the process including neutralization of the catalyst. said solid resin yielding homogeneous reaction products when heated together with a drying oil, which reaction products are soluble in common solvents if at least a certain minimum proportion of oil is employed, but gelatinous and insoluble if less than that minimum proportion is employed, said proportion being dependent on the viscosity of the oil employed.

10. An oil soluble resin which is solid at ordinary temperature and capable of undergoing further condensation on the application of heat, obtained by (1) maintaining para-tertiary-butylphenol and a substantial excess of formaldehyde over the equimoiecuiar quantity in contact for a prolonged period of time at moderate temperatures in the presence of a strong alkaline catalyst, whereby a quantity of formaldehyde corresponding with 1-2 mol. per each mol. of the phenol is compounded, (2) neutralizing the catalyst by acidifying the reaction mixture and (3) converting the thus obtained liquid condensation product into a solid resin by the application of heat.

11. A process of dissolving the product obtained according to claim 1 in a fatty oil and causing the two components to react by application of heat, whereby further condensation occurs with the formation of water.

12. A homogeneom reaction product formed by reacting together by the application of heat the product obtained according to claim 1 and a fatty oil. 1 1

- 13. A homogeneous reaction product formed by reacting together by the application of heat the productobtainedaccordingtoclaimlandaio drying oil.

14. A homogeneous reaction product formed by reacting together by the application of heat, the product obtained according to claim 1 and a bodied drying oil.

15. A homogeneous reaction product formed by reacting together below the polymerization temperature the product obtained according to claim 1 and a fatty oil. the reaction product obtained being distinguished by its substantially higher 50 viscosity as compared with the mere mixture of the two components.

'r norms. 

